Delustered regenerated cellulose



. 25 of the nature of w Patented June 2i, 1932 UNITED: srarssfrnrsnr em HENRY a. oannnnn, or wasnmeron, ms'rnrcr or oonmu.

' nntus'rnann meanness-m) cnLLuLosn I .Io Drawing.

This invention relates to delustered re enerated cellulose; and it comprises a met d of delustering artificial silk or rayon, threads, sheets, films, etc. made by precipita- 8 tion from alkaline cellulose solutions,- such as viscose, of a filament coming from a spinneret, wherein the alkaline solution is admixed prior to extrusion with a small prov ortion'of an alkaline solution of a resin, or

10 kc bod capable of co-precipitation with g the cell ose, the amount of the y sin bein 1 usually about 5 per cent of the ce ulose an the most advantageous resin being a toluene sulfo amid-resin; and it further com rises an article formed of precipitated cell ose containing a co-precipitated resinous body, advantageously a toluene sulfo amid resin, such as para toluene methylene sulfo amid, intimately dispersed therethrough in such a form as to give a slight haze or an oipalesoence to transmitted light; all as more ully hereinafter set forth and as claimed. h

Commercial forms of regenerated cellulose such as rayon yarn, and sheets and. films hatis commercially known as cellophane, etc. are 0 en-to several. objec tions. For one thin e thread or yarn is not of even level appearance. or another thing, the transparency and luster are greater than is usually desirable; a more silky a pearance being wanted. Still. another 0 1ection is that the material is more or less h groscopic and is not resistant to water. 'l he wet strength of rayon fabrics is considerably less than the dry strength.

And, probably because of the hy oscopic nature of the material, the electric .ties are not satisfactory; theresistance and dielectric properties are not considered good.

For this reason an extensive use of such thread in wire insulation or of sheets and films for other electrical purposes is pro-- cluded.

Attempts have been made to obviate these viscose solutions from which the regenerated cellulose is made; but these emulsions do not give satisfactory results. The appearance of the rayon thread and yarn is less even and level than with untreated viscose and the dry properobjections by emulsifying mineral oils in the Application filed October 25, 1889. Serial No. 402,5.

strength is considerably reduced while the wet strength is not improved. The use of emulsified mineral oils therefore, while it has been roposed, has not gone into extensive use. t is the object of the resent invention to produce an improved de uste'red regenerated cellulose of lessened hygroscopicit I have found that by the simple exp ient of incorporating into an alkaline oefiulose solution, such as viscose, prior to regeneration of the cellulose, body'capable of coprecipitation with cellulose in "opaque, finely divided form I can produce a certain amount of internal haze or opalescence which gives a more attractive thread.- Thread is delustered to an extent and in a way which makes it more nearly comparable with natural silk. The haze producmg body is advantageously of resinous nature. 7 The amount of which will ive the desired amount of delustering, electrical properties of the regenerated cellulose and improve the resistanceto the action of water,

and desirable in forming a. haze or opalescence.

After the addition of the alkaline resin solution, the subsequent operations are those used in the art of making rayon yarn or sheets or films from viscose or other alkaline solutions of cellulose,suph as copper'oxidammonia solutions.

To obtain the best results in the resent invention, the haze-producing su stance should be in clear solution in the viscose or other solution as it leaves the spinneret and a small amount of a coprecipitated resin also considerably improve the 15 So far as my, present knowledge extends,

should be precipitated during acidification.

' best t pe of haze.

By so doing, the precipitate is extremely fine, being of colloid fineness, and gives the In the usual operation of m mg thread, there is no time afforded for growth of the nuclei formed in precipitation into bodies of sensible size. The resent operation adds; to the uniformity 0 ap-' pearance or level appearance of the thread. The most attractive appearance I have secured has been with toluene sulfo amid resinsand particularly para toluene methylene sulfo amid. In making delustered viscose'silk under the present invention, using para toluene methylene sulfo amid, about 5 per cent of this material (on the weight of the cellulose) is dissolved in caustic soda to give a clear transparent solution. This solution. is admixed intimately with the viscose mass which is then extruded in the usual way into a salt solution or an acid solution to regenerate the cellulose as a filament or sheet. The precipitation 'of the cellulose throws out at the same time the dissolved resin in a white cloudy form, givin a slight internal haze to the dry and finisfied fiber, etc., making it more translucent than transparent and giving it an appearance by reflected light more nearly that of silk than the appearance of the untreated ra on. Viscose yarn produced by my process asgoodtensile stren 'h and an electric insulating value eater t an ordinary viscose yarn. Also my product is more water-resistant than ordinary viscose yarn, and consequently its wet strength is much higher.

When my new product is made in the form of threads or filaments the delustering efiect is of prime importance and the electrical insulating properties secondary, for in such form the main use of the product is the fabrication of textile materials. In such textile materials the appearance is of great commercial importance and the delustering effect is very desirable. On the other hand when the product is in the form of sheets or films, like the so-called cellophane, the improvephane sheet possessing very high water resistance may become the major consideration. To secure the maximum improvement in electrical and water resistance the amount of resin may be increased to about 10 per cent. In this case the product has the same dull or delustered appearance although it is not so attractive to the eye as that obtained using about 5 per cent of the resin. In making rayon thread for electrical insulation, a similar increase in the amount of incorporated I resin is desirable.

The present invention is an advance and an improvement upon some of my prior inventions in this art. In my .Patent No. 1,564,664 I describe and claim a film-forming composition comprising a solution of toluene sulphoamid aldehyde resins and organo-oxycellulose compounds of the cellulose ester and ether type. In my Patent No. 1,730,417 I describe and claim a cellulosic artificial filament containing an electrical non-conducting resin the said filament having improved electrical and films produced by the processes of these prior patents have a high and enduring gloss and do not have the delustered appearance of the products produced in accordance with the present invention,.theresin not being in the same form or condition. In my copendinsulating properties. The filaments ing application Ser/No. 322,094 I describe and claim processes of making delustered artificial silk from organo-oxy-cellulose compounds of-the cellulose ester and ether type. The present invention relates to a difierent process of making another type of artificial silk having a similar delustered appearance from cellulosic compounds of the viscose or regenerated cellulose type, the present process being particularly adapted to the production of regenerated cellulose com ositions.

My new products have a com ination of desirable roperties which readily suggest tothose skilled in the art various applications and uses which have been hitherto unobtainable with regenerated cellulose materials. I ma mention that the treated sheets produce by the present invention are useful in wrapping iron pipe to protect it from corrosion and passage of stray electrical currents stance iron pipe which is buried in the ground and used for carr ing petroleum, gas, and

other products. he present products are also useful in making telephone cables. My products s s h h sistance. when it is desired to have a cellophane sheet possessing very high water resistance to meet unusual or special conditions, sheets of regenerated cellulose produced by my present process may be varnished with a cellulose ester solution containing usually about two parts of para-toluene sulphoamid resins to one part of cellulose ester,both bein dissolved in suitable solvents. The so-coated sheets have an exceedingly high water resistance.

What I claim is 1. In delustering artificial silk of the regenerated cellulose type formed by the ex trusion process from alkaline solutionsof cellulose the process which comprises adding to an alkaline solution of cellulose a small proportion of an alkaline solution of a .resinous body capable of being precipitated in acid solution, said resinous ody being a resin of the toluene sulphoamid type, extruding the said mixture into an acid bath and coprecipitating the said resinous body and the cellulose, the said resinous body being precipitated out of solution as a fine haze.

2. In delustering artificial silk of the regenerated cellulose type formed by the exde'gree of water re-- ene sulphoamid resin, extruding the said 40 about 5 per cent of the weight of the threa 1, ,43 3 trusion process from alkaline solutions of I I cellulose the process which comprises addin to an allialine solution of cellulose a proportion of an alkaline solution of a tolumixture into an acid bath and coprecipit-ating the said toluene sulphoamid resin and the cellulose, the said toluene sulphoamid resin being precipitated out of solution as a i 10 fine haze.

3. As a new material an extruded body of a retgenerated cellulose compound containing I uni ormly distributed therem a haze-like suspension of a solid resinous body precipitated therein said solid body being a resin of the toluene sul hoamid type, the amount of suspended sohdbeing merely that which; will make the re enerated cellulose body translu-. cent; the said resinous body being one which so is soluble in alkaline s inning solutions but precipitable by acid so utions. Y

4, As a new type of delustered rayon a myon thread containing an acid precipitated, dispersed resinous solid, said resinous solid as being a resin of the toluene sulphoamid type,

. the amount of this dispersed solid being merely' sufiicient to give; an internal haze to the rayon.

5. A delustered regenerated cellulose ma- 80 terial containing a toluene sulphoamid con- .-densation product as a dispersoid phase, the said delustered re enerated celulose material being waterresistant and possessing improved electrical insulating properties.

85 6. As a new type of delustered ra on, a

rayon thread containing an acid rec; itated, dispersed resinous solid, sai resinous solid being a resin of the toluene sulphoamid type, the amount of this dispersed solid bein -7. A delustered thread containin about 5 per cent of dispersed toluene su phoamid resm.

8. In the manufacture ofre nerated cel- 4 lulose materials in the form 0 sheets, films,

filaments and threads, the process which comprises extruding an alkahne solution of cellulose containing a toluene sllphoamid type resin dissolved therein and coprecipitating the cellulose and the resin.

9. In the manufacture of regenerated cellulose materials in the form of sheets, films, filaments and threads, the rocess which comprises extruding an alkaline solution of cellulose containin a toluene sulphoamid t resin dissolved t erein into an acid bath and cop'recipitating the cellulose and the resin by the action of said acid bath.

10. In processes of making regenerated cellulose materials the step which comprises coprecipitating cellulose and a toluene sulphoamid type resin.

In testimony whereof, I have hereunto affixed my signature.

HENRY A. GARDNER.

CERTIFICATE or CORRECTION. Patent No. 1,864,426. r 1 June 21, 1932. I I HENRY A; GARDNER, '3

It is hereby certified that error appears in the printed specification of the" abovenumbered patent requiring correction as follows: Page 2, line 48,' strike out the syllable and words "phane sheet possessing very high" and insert instead ments in electrical insulation and; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office Signed and sealed this 4th day of October, A. o. 1932.

M. J. more. .7 I

g t; Acting-Gommialiwer otraten s, 

